A simple strategy to overcome concentration dependence of photoswitching properties in donor–acceptor Stenhouse adducts

Abstract

Photoswitchable donor–acceptor Stenhouse adducts (DASAs) have been reported to exhibit an undesirable concentration dependence, where photoswitching is greatly inhibited with increasing photochrome concentration. Here we show that the use of piperazine-based donor moieties eliminates this concentration dependence and results in complete, rapid and reversible photoswitching behaviour for first generation DASAs, even in chlorinated solvents. Structural data and computational studies reveal proton transfer during isomerisation to the terminal amine rather than the donor amine. The improvement in photoswitching efficiency is attributed to resultant differences in supramolecular association.